Dry etching method and method of manufacturing semiconductor device

ABSTRACT

There is provided a dry etching method for forming an insulating layer of SiO 2  or the like in a desired shape with a substantially infinite selection property with respect to Si 3 N 4  used as an etching stopper. As an etching gas a gas (HI, or a gas having a constitution of C x H y I z ) containing iodine in a molecule is added. Here, a mixing ratio (I/C) of iodine to carbon in the etching gas is 0.3≦(I/C)≦1.5. Alternatively, instead of the iodine-containing gas the gas containing chlorine or bromine as the same halogen element is used. Since iodine, chlorine, or bromine contained in the etching gas generates a low vapor pressure material on Si 3 N 4 , Si 3 N 4  etching is completely prohibited. Since no low vapor pressure material is generated on SiO 2  or SiOF as a material to be etched, a high etching rate can be obtained.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a dry etching method and method of manufacturing a semiconductor device, and more particularly to a dry etching method for forming a semiconductor device structure on a semiconductor wafer.

[0003] 2. Description of the Related Art

[0004] In a semiconductor device, a silicon oxide (hereinafter referred to SiO₂ ) layer is widely used as an interlayer layer where a contact hole (via hole), a wiring groove, and the like is formed by a dry etching process.

[0005] In the dry etching process, as a etching stopper film (film for selectively stopping the progress of etching in a position thereof) used for an etching depth to be uniform, a silicon nitride (hereinafter referred to Si₃N₄) film is most frequently used. This is because the film is the most superior film as the etching stopper film of the insulating layer in view of stability as the film, compatibility with the SiO₂ layer, heat resistance, insulating property, and other general properties.

[0006] Moreover, a gas for general use in SiO₂ etching at present is a gas mainly comprising C_(x)F_(y) (x and y are positive integers). In addition, argon (Ar), oxygen (O₂), carbon monoxide (CO) and the like may be added to this main gas as occasion demands.

[0007] As described above, Si₃N₄ is most frequently used as the etching stopper of the insulating layer, but sufficiently high selection property can not be obtained in an SiO₂ etching process which is generally performed at present.

[0008] There are two reasons for this with regard to a semiconductor device structure. The first reason is that the contact hole used in recent years is remarkably high in aspect ratio, a deposition component does not easily enter a hole bottom part, and sufficient protection effect is not obtained. The second reason is that Si₃N₄ has the insulating property, but dielectric constant of Si₃N₄ is higher than that of SiO₂, and therefore, Si₃N₄ remaining outside the contact hole as a part of the insulating layer must be as thin as possible (about 50 nm). Consequently, the film thickness of the Si₃N₄ as a etching stopper film becomes inevitably thin as about 50 nm, and therefore, the required selection property is a remarkably high value such as the order of 50 to 100. By these reasons, as a selection ratio to Si₃N₄ in insulation layer etching, a substantially infinite selection ratio is required, but it is remarkably difficult to achieve the ratio in a current etching method.

[0009] A reason why the high selection property cannot be obtained with respect to Si₃N₄ in the conventional etching method in which the C_(x)F_(y) gas is used as the main gas is as follows. When an active species of the gas contacts Si₃N₄, first C extracts N on a surface, F attacks freed Si and the etching supposedly proceeds in this pattern. Since both (CN)x and SiF₄ are high vapor pressure materials, on occurrence of a reaction the etching proceeds.

SUMMARY OF THE INVENTION

[0010] Wherefore, one object of the present invention is to provide an effective dry etching method, which solves the aforementioned related-art problems.

[0011] Another object of the present invention is to provide a method of manufacturing a semiconductor device using the effective dry etching method.

[0012] According to the present invention, there is provided a dry etching method which comprises a step of etching an insulating layer of a semiconductor device structure using a silicon nitride represented by Si₃N₄ as an etching stopper under an etching gas atmosphere. The etching gas includes a gas containing iodine in a molecule. The insulating layer may be a silicon oxide represented by SiO₂ layer, a fluorine-containing silicon oxide layer, or an organic SOG layer or another silicon oxide insulating layer. Additionally, a mixing ratio (I/C) of iodine to carbon in the etching gas, that is, a ratio of number (quantity) of iodine atoms to number (quantity) of carbon atoms in the etching gas is 0.3≦(I/C)≦1.5, that is, the ratio (I/C) is 0.3 or more, and 1.5 or less. Here, the iodine-containing gas can be an HI gas or a gas having a constitution of C_(x)H_(y)I_(z) (x, y and z are positive integers).

[0013] According to another aspect of the present invention, there is provided a dry etching method which comprises a step of etching an insulating layer of a semiconductor device structure using a silicon nitride film represented by Si₃N₄ as an etching stopper under an etching gas atmosphere. The etching gas includes a gas containing chlorine or bromine in a molecule. The insulating layer may be a silicon oxide represented by SiO₂ layer, a fluorine-containing silicon oxide layer, or an organic SOG layer or another silicon oxide insulating layer. Additionally, a mixing ratio (Cl (or Br)/C) of chlorine or bromine to carbon in the etching gas is 0.3≦(Cl (or Br)/C)≦1.5. That is, a ratio of number (quantity) of chlorine atoms or bromine atoms to number (quantity) of carbon atoms in the etching gas is 0.3 or more, and 1.5 or less. Here, the gas containing chlorine or bromine can be a Cl₂ gas, an HCl gas, a gas having a constitution of C_(x)H_(y)Cl (x, y and z are positive integers), a gas having a constitution of C_(x)Cl_(z) (x, and z are positive integers), for example, CCl₄, a Br₂ gas, an HBr gas, or a gas having a constitution of C_(x)H_(y)Br_(z) (x, y and z are positive integers)

[0014] According to further aspect of the present invention, there is provided a method of manufacturing a semiconductor device which comprises steps of forming a wiring layer on a semiconductor substrate via an insulator, forming a silicon nitride film represented by Si₃N₄ on the wiring layer, forming an insulating layer on the silicon nitride film, and forming a contact hole in the insulating layer by a dry etching method. The dry etching method includes a step of etching the insulating layer by using the silicon nitride film as an etching stopper under an etching gas atmosphere. The etching gas includes a gas containing iodine, chlorine or bromine in a molecule, and a mixing ratio ((I, Cl or Br)/C) of iodine, chlorine or bromine to carbon in the etching gas is 0.3 or more, and 1.5 or less.

[0015] According to yet further aspect of the present invention, there is provided a method of manufacturing a semiconductor device which comprises steps of forming a pair of gate electrode structures on a semiconductor substrate via gate insulating films, covering the gate electrode structures and a space between the gate electrode structures with a silicon nitride film represented by Si₃N₄ continuously, forming an insulating layer on the silicon nitride film, and forming a contact hole in the insulating layer between the gate electrode structures by a dry etching method. The dry etching method includes a step of etching the insulating layer by using the silicon nitride represented by Si₃N₄ film as an etching stopper under an etching gas atmosphere. The etching gas includes a gas containing iodine, chlorine or bromine in a molecule, and a mixing ratio ((I, Cl or Br)/C) of iodine, chlorine or bromine to carbon in the etching gas is 0.3 or more, and 1.5 or less.

[0016] Furthermore, the aforementioned etching method is preferably used when a contact hole with an aspect ratio of 20 or less is formed in the insulating layer.

[0017] In this case, etching is performed by the etching gas from the surface of the insulating layer to reach Si₃N₄ so that the contact hole can be formed in the insulating layer. Alternatively, in a two-step etching method which comprises performing etching from the surface of the insulating layer with a first etching gas to form an upper part of the contact hole, and subsequently performing the etching with a second etching gas until Si₃N₄ is reached to form a lower part of the contact hole; the aforementioned etching gas including iodine, chlorine or bromine can be used as the second etching gas.

[0018] According to the dry etching method of the present invention, iodine contained in the etching gas forms CNI which is a low vapor pressure material on Si₃N₄, and inhibits the etching of the Si₃N₄. Also, when the chlorine or bromine-containing gas is used, CNCl or CNBr, that is, a relatively low vapor pressure material is formed to inhibit the etching of the Si₃N₄.

[0019] In either case, since no low vapor pressure material is generated on SiO₂ as the material to be etched, SiOF whose dielectric constant is lowered by containing fluorine in silicon oxide, or organic SOG, a high etching rate can be obtained.

[0020] Moreover, when a CxHyFz (x, y and z are positive integers) gas used in recent years is added, NH₃ with a higher vapor pressure is generated, and it is therefore difficult to keep a high selection property with respect to Si₃N₄. However, even in this case, when an iodine-containing gas is used, NH₄I with a low vapor pressure is formed to inhibit the etching of the Si₃N₄ film.

[0021] The reason why the ratio (I/C) of iodine to carbon in the etching gas is set in a range of 0.3≦(I/C)≦1.5 is that an effect of the range includes dependence on an aspect ratio, and with a larger aspect ratio the I/C ratio needs to be set to be high. Specifically, according to various experiments/inspections by the present inventors, when flat and large patterns such as a pad pattern are etched, a sufficient etching inhibition effect is obtained at I/C=0.3. However, in order to obtain a sufficient etching inhibition effect in Si₃N₄ in a contact hole bottom part with an aspect ratio of 20 (e.g., hole diameter of 0.15 μm/depth of 3.0 μm), which is a largest aspect ratio in a presently used semiconductor device, I/C=1.5 is necessary. Moreover, it has been confirmed by the experiments that the etching inhibition effect depends on the aspect ratio rather than on the hole diameter. This respect will be described in an embodiment.

[0022] Furthermore, it has been confirmed that even when instead of the iodine-containing gas the gas containing chlorine or bromine as the same halogen element is used, the similar action/effect can be produced.

BRIEF DESCRIPTION OF THE DRAWINGS

[0023]FIG. 1 shows diagrams of a first embodiment of the present invention: FIG. 1A is a sectional view of a sample structure; FIG. 1B is a chart showing a relation between an I/C ratio and an Si₃N₄ etching rate; and FIG. 1C is a chart showing a relation between an aspect ratio and an S value.

[0024]FIG. 2 shows diagrams of a second embodiment of the present invention: FIG. 2A is a sectional view before plasma etching; and FIG. 2B is a sectional view after the plasma etching.

[0025]FIG. 3 shows diagrams of a third embodiment of the present invention: FIG. 3A is a sectional view before the plasma etching; and FIG. 3B is a sectional view after the plasma etching.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] Embodiments of the present invention will next be described with reference to the drawings.

[0027] A sectional view of a sample of a first embodiment is shown in FIG. 1A. Specifically, FIG. 1A shows the sample constituted of forming Si₃N₄ 12 and SiO₂ 13 in sequence on an underlying wiring layer 11 formed on an insulator 10 such as a field oxide layer provided on a major surface on a semiconductor substrate 9, and using a pattern of a photoresist (PR) 14 as a mask and Si₃N₄ 12 as an etching stopper to subject SiO₂ 13 to a dry etching which is an anisotropic etching, in order to form a contact hole reaching the underlying wiring layer.

[0028] A film thickness of PR is 700 nm (nano-meter), film thickness of SiO₂ is 1500 nm, and film thickness of Si₃N₄ is 50 nm.

[0029] A process gas I/C ratio and Si₃N₄ etching rate during dry etching using this sample were investigated. In the sample, since resolution to a hole-diameter of 0.3 μm is achieved by KrF exposure, the aspect ratio after the etching is 5.

[0030] In a case of changing the process gas I/C ratio and measuring the Si₃N₄ etching rate of the hole bottom part, when the I/C ratio was increased, the Si₃N₄ etching rate of the hole bottom part was lowered. In the present structure, the etching did not proceed at all at the I/C ratio of 0.65. A relation between the process gas I/C ratio and the Si₃N₄ etching rate is shown in FIG. 1B. Here, an I/C ratio at which the Si₃N₄ etching rate of the hole-bottom part becomes zero (0) is defined as an S value.

[0031] By variously changing the SiO₂ film thickness and hole diameter and checking a relation between the aspect ratio and the S value, as shown in FIG. 1C, it has been found that there is a substantially directly proportional relation (S value=0.06×aspect ratio+0.3). Here, since the aspect ratio substantially necessary in the semiconductor device is 20 or less, it has been found that the I/C ratio effective for a high selection etching to Si₃N₄ is in a range of 0.3 to 1.5.

[0032] A second embodiment of the present invention will next be described with reference to FIG. 2. There is shown a case in which a 0.3 μm wide groove for groove wiring is formed by PR (resist mask) 14. A shape before the etching is shown in FIG. 2A.

[0033] For the etching stopper, Si₃N₄ with a film thickness of 50 nm was formed, and SiO₂ with a film thickness of 1500 nm was formed on the stopper as an interlayer.

[0034] The photoresist mask (PR) was provided with a film thickness of 700 nm, and the resolution to a width of 0.3 μm was achieved by KrF exposure. The photoresist was subjected to a heat treatment of 120° C. by baking after a development treatment.

[0035] An apparatus for use in anisotropic etching was a general parallel flat plate RIE apparatus, and etching conditions were C₄F₈/CO/Ar/HI=30/70/300/120 (sccm), pressure of 20 mTorr, and stage temperature of 20° C. The I/C ratio in these conditions is 0.63. According to the present conditions, SiO₂ etching rate: 620 nm/min, and SiO₂/PR selection ratio is 12.

[0036] By setting an over etch amount to 50% with respect to the SiO₂ film thickness, an etching time was set.

[0037] A schematic view of an etched shape is shown in FIG. 2B. No shave of Si₃N₄ of the hole bottom part was confirmed, and deposition of 18 nm was found. Even by setting the over etch amount to 100% and setting the etching time, only a deposited film thickness increased, and no shave of Si₃N₄ of the hole bottom part was confirmed. Moreover, a critical dimension (CD) difference indicating a dimension change amount after the etching was satisfactory within ±4 nm.

[0038] Additionally, thereafter, by removing the part of Si₃N₄ 12 exposed to the bottom part by wet etching or the like, the contact hole is completed to reach the underlying wiring layer 11.

[0039] A third embodiment of the present invention will next be described with reference to FIG. 3. In the third embodiment, a self-aligned contact (SAC) with a hole dimension of 0.20 μm diameter or width is formed in the resist mask. A shape before etching is shown in FIG. 3A.

[0040] In FIG. 3A, a pair of gate electrodes is formed on a semiconductor substrate 15 via a gate insulating film 17, in which Poly-Si with a film thickness of 200 nm is formed as a lower film 18, and WSi with a film thickness of 200 nm is formed as an upper film 19. A source/drain area 16 is formed in a semiconductor substrate part between the gate electrodes.

[0041] The gate electrodes and the part between the gate electrodes are coated with Si₃N₄ 12 having a film thickness of 250 nm directly on the gate electrodes and about 50 nm on the side wall parts and on the part between the gate electrodes, and SiO₂ 13 is formed in a film thickness of 1200 nm. The photoresist mask 14 had a film thickness of 600 nm, and resolution to a diameter of 0.20 μm was achieved by KrF exposure.

[0042] The apparatus for use in the etching was the general parallel flat plate RIE apparatus, and conditions of the dry etching as the anisotropic etching were C₄F₈/Ar/O₂/CH₂F₂/HI=30/200/3/5/60 (sccm), pressure of 20 mTorr, and stage temperature of 20° C. The I/C ratio in these conditions is 0.48.

[0043] According to the present conditions, SiO₂ etching rate: 560 nm/min, and the SiO₂/PR selection ratio is 15. By setting the over etch amount to 50% with respect to the SiO₂ film thickness, the etching time was set. A schematic view of the etched shape is shown in FIG. 3B. A shave of Si₃N₄ in a gate electrode shoulder part was confirmed by about 10 nm. In this case, by setting a flow rate of HI to be added to 72 sccm, and setting the I/C ratio to 0.58, no shave amount of Si₃N₄ of the gate electrode shoulder part was confirmed.

[0044] For the gate shoulder part during SAC etching, since a sputter-efficiency is high and etching easily occurs by an ion physical action, a generation efficiency of an etching inhibitor needs to be raised. According to the experiment, by increasing the HI flow rate by at least 20% with respect to the S value of FIG. 1C, the Si₃N₄ etching could completely be inhibited. Additionally and thereafter, by removing Si₃N₄ and thin insulating film 17 on the source/drain area 16 by the dry etching using a three-element gas of CHF₃/O₂/Ar, the contact hole is completed to reach the source/drain area 16.

[0045] Additionally, in the aforementioned embodiments, the HI gas is illustrated as an iodine-containing gas, but a gas having a constitution of C_(x)H_(y)I_(z) (x, y and z are positive integers) may also be used similarly.

[0046] Moreover, in the first and other embodiments, the gas containing iodine in a molecular is illustrated as the etching gas, but a gas containing chlorine or bromine in a molecular by Cl₂ gas, HCl gas, a gas having a constitution of C_(x)H_(y)Cl_(z) (x, y and z are positive integers), a gas having a constitution of C_(x)Cl_(z) (x, and z are positive integers), for example, CCl₄, a Br₂ gas, an HBr gas, or a gas having a constitution of C_(x)H_(y)Br_(z) (x, y and z are positive integers) may also be used similarly as the etching gas. In this case, I/C of the abscissa of FIG. 1B changes to Cl (or Br)/C.

[0047] Moreover, SiO₂ has been illustrated as the insulating layer subjected to the dry etching, but a case in which the insulating layer subjected to the dry etching is SiOF is similar to the aforementioned embodiment. Furthermore, for the insulating layer to be subjected to the dry etching, organic SOG constituted only by attaching a methyl group or the like to silicon oxide of inorganic is substantially the same as silicon oxide of inorganic in an etching mechanism, and is therefore similar to the aforementioned embodiment. Additionally, examples of organic SOG include metyle silsesquioxane (MSQ), hydride organo siloxane polymer (HOSP), and the like.

[0048] Furthermore, in the embodiment, the etching was performed by the etching gas described in the embodiment of the present invention from the upper surface of the insulating layer 13 to reach Si₃N₄ film 12.

[0049] However, when it is difficult to establish both the etching of a deep contact hole and the selection property with Si₃N₄, another etching gas such as a four-element gas of C₄F₈/CO/Ar/O₂ containing none of iodine, chlorine and bromine is used in a former-half etching, and the etching gas of the present invention can be used in a latter-half etching in which the selection property with Si₃N₄ raises a problem.

[0050] As described above, by adding an iodine-containing gas (HI, or a gas having a constitution of C_(x)H_(y)I_(z)) as the etching gas of the insulating layer of SiO₂ or the like in such a manner that a ratio (I/C) of iodine to carbon in the etching gas is in a range of 0.3≦(I/C)≦1.5, and performing dry etching, an insulating layer etching of a substantially infinite selection ratio with respect to Si₃N₄ is possible. Here, even when instead of the iodine containing gas the gas containing chlorine or bromine as the same halogen element is used, the similar effect can be produced.

[0051] In the method of the present invention, iodine contained in the etching gas forms CNI as a low vapor pressure material on Si₃N₄, and therefore inhibits the etching of Si₃N₄ using as an etching stopper film. Moreover, when the chlorine or bromine containing gas is used, CNCl or CNBr, that is, a relatively low vapor pressure material is formed to inhibit the etching of Si₃N₄ using as an etching stopper film.

[0052] Moreover, when a CxHyFz gas used in recent years is added, NH₃ with a higher vapor pressure is generated, and it is therefore difficult to keep a high selection property with respect to Si₃N₄. However, even in this case, when the iodine containing gas is used, NH₄I with a low vapor pressure is formed on Si₃N₄, and therefore inhibits the etching of Si₃N₄ using as an etching stopper film. 

What is claimed is:
 1. A dry etching method comprising a step of: etching an insulating layer of a semiconductor device structure using a silicon nitride film as an etching stopper under an etching gas, said etching gas including a gas containing iodine in a molecule.
 2. The dry etching method according to claim 1 , wherein a mixing ratio (I/C) of iodine to carbon in said etching gas is 0.3 or more, and 1.5 or less.
 3. The dry etching method according to claim 1 , wherein said gas containing iodine is an HI gas or a gas having a constitution of C_(x)H_(y)I_(z) (x, y and z are positive integers)
 4. A dry etching method comprising a step of: etching an insulating layer of a semiconductor device structure using a silicon nitride film as an etching stopper under an etching gas, said etching gas including a gas containing chlorine or bromine in a molecule.
 5. A dry etching method according to claim 4 , wherein a mixing ratio (Cl(or Br)/C) of chlorine or bromine to carbon in said etching gas is 0.3 or more, and 1.5 or less.
 6. A dry etching method according to claim 4 , wherein said gas containing chlorine or bromine is a Cl₂ gas, an HCl gas, a gas having a constitution of C_(x)H_(y)Cl_(z) (x, y and z are positive integers), a gas having a constitution of C_(x) Cl_(z) (x, and z are positive integers), a Br₂ gas, an HBr gas, or a gas having a constitution of C_(x)H_(y)Br_(z) (x, y and z are positive integers).
 7. A dry etching method according to any one of claims 1 to 6 , wherein said insulating layer is a silicon oxide layer, a fluorine-containing silicon oxide layer, or an organic SOG layer.
 8. A dry etching method according to any one of claims 1 to 7 , wherein a contact hole is formed in said insulating layer by using said etching gas.
 9. The dry etching method according to claim 8 , wherein said etching step using said etching gas is performed from the surface of said insulating layer until said silicon nitride film.
 10. The dry etching method according to claim 8 , wherein a first etching step using a etching gas is performed from the surface of said insulating layer to a predetermined depth, and subsequently, a second etching step using said etching gas is performed from said predetermined depth of said insulating layer until said silicon nitride film.
 11. A method of manufacturing a semiconductor device comprising steps of: forming a wiring layer on a semiconductor substrate via an insulator; forming a silicon nitride film on said wiring layer; forming an insulating layer on said silicon nitride film; and, forming a contact hole in said insulating layer by a dry etching method; wherein, said dry etching method comprises a step of: etching said insulating layer by using said silicon nitride film as an etching stopper under an etching gas, said etching gas including a gas containing iodine, chlorine or bromine in a molecule, and a mixing ratio (I,Cl or Br)/C) of iodine, chlorine or bromine to carbon in said etching gas is 0.3 or more, and 1.5 or less.
 12. A method of manufacturing a semiconductor device comprising steps of: forming a pair of gate electrodes on a semiconductor substrate via gate insulating films; covering said gate electrodes and a space between said gate electrode structures with a silicon nitride film, continuously; forming an insulating layer on said silicon nitride film; and, forming a contact hole in said insulating layer between said gate electrodes by a dry etching method; wherein, said dry etching method comprises a step of: etching said insulating layer by using said silicon nitride film as an etching stopper under an etching gas, said etching gas including a gas containing iodine, chlorine or bromine in a molecule, and a mixing ratio (I,Cl or Br)/C) of iodine, chlorine or bromine to carbon in said etching gas is 0.3 or more, and 1.5 or less. 